US20210380805A1 - Isocyanate-polyamide block copolymers - Google Patents
Isocyanate-polyamide block copolymers Download PDFInfo
- Publication number
- US20210380805A1 US20210380805A1 US17/286,827 US201917286827A US2021380805A1 US 20210380805 A1 US20210380805 A1 US 20210380805A1 US 201917286827 A US201917286827 A US 201917286827A US 2021380805 A1 US2021380805 A1 US 2021380805A1
- Authority
- US
- United States
- Prior art keywords
- diisocyanate
- thermoplastic polyamide
- dicarboxylic acid
- iii
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006147 copolyamide elastomer Polymers 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 157
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 109
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 94
- 229920006345 thermoplastic polyamide Polymers 0.000 claims abstract description 85
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 44
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- 150000001735 carboxylic acids Chemical group 0.000 claims abstract description 9
- 239000002879 Lewis base Substances 0.000 claims abstract description 7
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 35
- -1 C12 dicarboxylic acids Chemical class 0.000 claims description 34
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- 239000006260 foam Substances 0.000 claims description 12
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 12
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- 239000000126 substance Substances 0.000 description 9
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 8
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 8
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- 239000012948 isocyanate Substances 0.000 description 8
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
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- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical class O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
- B29C48/144—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration at the plasticising zone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
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- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
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- C08G18/48—Polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- C08L2203/14—Applications used for foams
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C08L2203/30—Applications used for thermoforming
Definitions
- the present invention relates to a thermoplastic polyamide obtainable or obtained through the reaction of at least the components (i), (ii), and (iii): a composition comprising a polymeric compound having two carboxylic acid moieties (i); a dicarboxylic acid composition comprising at least one dicarboxylic acid (ii); a diisocyanate composition comprising at least one diisocyanate (iii).
- the invention additionally relates to a process for producing the thermoplastic polyamide and the use thereof and to a tandem reactive extruder.
- thermoplastic block copolymers such as thermoplastic polyurethane (TPU), thermoplastic polyether esters, and polyester esters (TPEEs) have been known for a long time. They form on a hard phase derived from an often aromatic, difunctional building block such as a diisocyanate or a dicarboxylic acid, a short-chain diol, and a soft, elastic phase derived from a long-chain difunctional polyol.
- Polyamide block copolymers (TPAs) such as polyether amide (for example Pebax), consist of an aliphatic polyamide building block and a polyetherol unit, which are in most cases introduced into the polymer through terminal amine groups.
- Polyether amides rank among the highest-cost thermoplastic elastomers and have advantages over TPUs in their thermal stability and “snapback” (spontaneous elasticity with high dynamic recovery), but are significantly more expensive and are complicated to use in production. There is consequently the need for a product that combines the properties of TPUs (continuous production, high elasticity and tensile strength) and TPAs (good thermal stability and resistance to solvents, snapback), allows a less complicated synthesis, and is cost-effective to use in production.
- EP 2 700 669 A1 A mixed form from polyurethane (PU) and polyamide (PA) is described in EP 2 700 669 A1, which relates to a plastically deformable rigid polyurethane-polyamide foam with a closed-cell factor of less than 70%, and a process for its production in which organic polyisocyanate is reacted with one or more polymeric compounds having at least two hydrogen atoms reactive towards isocyanates and one or more carboxylic acids having a functionality of at least 2, with the use of a catalyst, to form a rigid polyurethane-polyamide foam.
- PU polyurethane
- PA polyamide
- the carboxylic acids used are, in particular, aliphatic dicarboxylic acids having 2 to 30 carbon atoms;
- the polymeric compounds having at least two hydrogen atoms reactive towards isocyanates are polyether polyols with a polypropylene oxide content of not less than 50% by weight based on the alkylene oxide content in the polyalkylene oxide polyol.
- they do not have the degree of cross-linking of thermoplastically processable products, which likewise are not block copolymers.
- pure mixtures of TPU and PA such as PA6, PA6.6 or PA12
- PA6 PA6, PA6.6 or PA12
- PA6 PA6, PA6.6 or PA12
- These are blends produced from granule mixtures, normally in an extruder or kneader.
- TPU predominates tend towards TPU properties
- PA predominates towards polyamide properties.
- the absence of a chemical bond between the components means their use is compromised by this shortcoming, consequently the product properties are little better than those of pure TPU or PA.
- the object of the present invention was thus to provide a production process and a polymer with which the above disadvantages can be avoided and which combine the properties of TPUs and TPAs.
- thermoplastic polyamide obtainable or obtained through the reaction of at least the components (i), (ii), and (iii):
- composition comprising a polymeric compound having two carboxylic acid moieties
- the composition in accordance with (i) comprises 95% by weight, preferably 99% by weight, of one or more polymeric compounds each having two carboxylic acid moieties, based on the total weight of the composition in accordance with (i).
- the dicarboxylic acid composition in accordance with (ii) comprises 95% by weight, preferably 99% by weight, of one or more dicarboxylic acids and/or dicarboxylic anhydrides, based on the total weight of the dicarboxylic acid composition in accordance with (ii).
- the diisocyanate composition in accordance with (iii) comprises 95% by weight, preferably 99% by weight, of one or more diisocyanates, based on the total weight of the diisocyanate composition in accordance with (iii).
- thermoplastic polyamide the composition comprising a polymeric compound having two carboxylic acid moieties in accordance with (i) is obtained or obtainable through the reaction of the components (ia) and (ib):
- the polymeric compound having two carboxylic acid moieties preferably has no free hydroxyl groups other than the OH groups present in the COOH groups.
- a diol composition comprising a dihydric polyester diol or polyether diol is used.
- Suitable dihydric polyester diols are known per se to those skilled in the art.
- Polyester diols may be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
- dicarboxylic acids examples include: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids may be used either individually or in admixture with one another.
- the free dicarboxylic acids it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylate esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides.
- dicarboxylic acid mixtures of succinic acid, glutaric acid, and adipic acid in quantity ratios of, for example, 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
- dihydric alcohols are: ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol.
- polyester diols derived from lac-tones for example ⁇ -caprolactone
- hydroxycarboxylic acids for example ⁇ -hydroxycaproic acid
- the polyester diols may be prepared by polycondensation of the organic, for example aromatic and preferably aliphatic dicarboxylic acids and/or derivatives and dihydric alcohols without catalyst or preferably in the presence of esterification catalysts, ideally in an atmosphere of inert gas, for example nitrogen, carbon monoxide, helium, argon, etc., in a melt at temperatures of 150 to 250° C., preferably 180 to 220° C., optionally under reduced pressure, down to the desired acid number which is preferably less than 10, more preferably less than 2.
- inert gas for example nitrogen, carbon monoxide, helium, argon, etc.
- the esterification mixture undergoes polycondensation at the above-mentioned temperatures down to an acid number of 80 to 30, preferably 40 to 30, under standard pressure and subsequently under a pressure of less than 500 mbar, preferably 50 to 150 mbar.
- esterification catalysts that may be used are iron catalysts, cadmium catalysts, cobalt catalysts, lead catalysts, zinc catalysts, antimony catalysts, magnesium catalysts, titanium catalysts, and tin catalysts in the form of metals, metal oxides or metal salts.
- the polycondensation may also be carried out in the liquid phase in the presence of diluents and/or entraining agents, for example benzene, toluene, xylene or chlorobenzene, for removal of the water of condensation by azeotropic distillation.
- diluents and/or entraining agents for example benzene, toluene, xylene or chlorobenzene
- the organic dicarboxylic acids and/or derivatives and dihydric alcohols advantageously undergo polycondensation in a molar ratio of 1:1 to 1.8, preferably 1:1.05 to 1.2.
- the polyester diols used have a functionality of 2 and, for example, a number-average molecular weight of 480 to 3000 g/mol, preferably 1000 to 3000 g/mol.
- Suitable dihydric polyether polyols are known per se to those skilled in the art.
- Polyetherols are prepared by known processes, for example by anionic polymerization with alkali metal hydroxides or alkali metal alkoxides as catalysts and with addition of at least one starter molecule comprising 2 to 8 reactive hydrogen atoms in bonded form, or through cationic polymerization with Lewis acids such as antimony pentachloride or boron fluoride etherate or through bases, for example potassium hydroxide, from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
- Suitable alkylene oxides are, for example, 1,3- and 1,2-propylene oxide, 1,2- and 2,3-butylene oxide, and ethylene oxide.
- tetrahydrofuran monomer may be used.
- the dihydric polyester diol or polyether diol which comprises the diol composition in accordance with (ia), is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyadipates, polycarbonates/polycarbonate diols, and polycaprolactones and polytetrahydrofuran (PTHF), preferably PTHF, with the PTHF preferably having a number-average molecular weight Mn in the range from 500 to 3000 g/mol, further preferably in the range from 500 to 1500 g/mol.
- PTHF polytetrahydrofuran
- a dicarboxylic acid composition is used.
- the dicarboxylic acid composition comprises one or more dicarboxylic acids and/or one or more dicarboxylic acid derivatives.
- dicarboxylic acid preference is given to organic dicarboxylic acids having 2 to 12 carbon atoms, further preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms.
- dicarboxylic acids that may be used are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids may be used either individually or in admixture with one another.
- dicarboxylic acids instead of, or in addition to, the free dicarboxylic acids it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylic anhydrides, which may likewise be used individually or in admixture with one another, and also mixtures comprising free dicarboxylic acids and dicarboxylic acid derivatives.
- dicarboxylic anhydrides which may likewise be used individually or in admixture with one another, and also mixtures comprising free dicarboxylic acids and dicarboxylic acid derivatives.
- the dicarboxylic acid composition in accordance with (ib) comprises at least one dicarboxylic acid or one dicarboxylic anhydride, with the dicarboxylic acid or dicarboxylic anhydride preferably selected from the group consisting of C2 to C12 dicarboxylic acids and the anhydrides thereof, further preferably from the group consisting of C4 to C8 dicarboxylic acids and the anhydrides thereof, further preferably at least 1,4-butanedioic acid (succinic acid) and succinic anhydride.
- the composition comprising a polymeric compound having two carboxylic acid moieties in accordance with (i) comprises at least one polyester dicarboxylic acid, polycarbonate dicarboxylic acid or polyether dicarboxylic acid, with the polyester, polycarbonate or polyether component preferably selected from the group of dihydric polyesters, polycarbonates, and polyethers, preferably from the group consisting of polyethylene glycol, polypropylene glycol, polyadipates, polycarbonates/polycarbonate diols, and polycaprolactones and polytetrahydrofuran (PTHF), preferably PTHF, with the PTHF preferably having a number-average molecular weight Mn in the range from 500 to 3000 g/mol, further preferably in the range from 500 to 2000 g/mol.
- PTHF polytetrahydrofuran
- the polymeric compound having two carboxylic acid moieties comprises preferably at least HOOC—(CH 2 ) x COO-PTHF-OOC—(CH 2 ) y —COOH, where x and y are each independently an integer in the range from 1 to 10, preferably in the range from 1 to 5, further preferably in the range 1 to 3, with the polymeric compound having two carboxylic acid moieties further preferably comprising at least HOOC—(CH 2 ) 2 —COO-PTHF-OOC—(CH 2 ) 2 —COOH.
- a dicarboxylic acid composition is likewise used, with the dicarboxylic acid composition comprising one or more dicarboxylic acids.
- the dicarboxylic acid preference is given to organic dicarboxylic acids having 2 to 12 carbon atoms, further preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms.
- dicarboxylic acids that may be used are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids may be used either individually or in admixture with one another.
- the dicarboxylic acid composition in accordance with (ii) comprises at least one dicarboxylic acid, preferably selected from the group of C2 to C12 dicarboxylic acids, further preferably from the group of C4 to C8 dicarboxylic acids, further preferably at least 1,6-hexanedioic acid (adipic acid).
- a diisocyanate composition is used.
- the diisocyanate composition here comprises at least one diisocyanate.
- the diisocyanate composition may also comprise two or more diisocyanates.
- Diisocyanates that may be used are aliphatic, cycloaliphatic, araliphatic, and/or aromatic diisocyanates. Specific examples include the following aromatic isocyanates: 2,4-tolylene diisocyanate, mixtures of 2.4- and 2,6-tolylene diisocyanate (TDI), 4,4′-, 2,4′-, and/or 2,2′-diphenylmethane diisocyanate (MDI), mixtures of 2,4′- and 4,4′-diphenylmethane diisocyanate, urethane-, carbodiimide- or uretonimine-modified liquid 4,4′- and/or 2,4-diphenylmethane diisocyanate, 4,4′-diisocyanatodiphenylethane, mixtures of monomeric methylene diphenyl diisocyanates, and higher polycyclic homologs of methylene diphenyl diisocyanates (polymeric MDI), (1,2)
- Aliphatic diisocyanates used are customary aliphatic and/or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta-, and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and/or 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-, 2,4′- and/or 2,2′-dicyclohexylmethane diisocyanate.
- the diisocyanate composition in accordance with (iii) comprises at least one diisocyanate selected from the group consisting of 2,2′-diphenylmethane diisocyanate (2,2′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), hexamethylene 1,6-diisocyanate (HDI), and 4,4′-, 2,4′-, and 2,2′-methylenedicyclohexyl diisocyanate (H12MDI), naphthylene diisocyanate NDI, tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), para-diphenyl diisocyanate (PDI), preferably at least MDI.
- 2,2′-diphenylmethane diisocyanate (2,2′-MDI)
- aromatic diisocyanates are used.
- the use of an aromatic diisocyanate yields partially aromatic amide block copolymers with further-improved thermal stability.
- the diisocyanate composition in accordance with (iii) may also be used in the form of a prepolymer, preferably a prepolymer having two free isocyanate groups, derived from at least one diisocyanate and at least one polyol, preferably a polyol having two terminal hydroxyl groups.
- a prepolymer allows the additional incorporation of urethane groups into the block copolymer in controllable proportions, through which it is possible, for example, to modify the properties of the polymer or increase its molecular weight.
- Diisocyanate prepolymers are obtainable by reacting an excess of the above-described diisocyanates, for example at temperatures from 30 to 150° C., preferably at temperatures from 50 to 120° C., most preferably at approximately 80° C., with polyols to form the prepolymer.
- the preparation of the prepolymers according to the invention is preferably carried out using diisocyanates and commercially available polyols based on polyesters, derived for example from adipic acid, or polyethers, derived for example from ethylene oxide and/or propylene oxide, with the polyols preferably having two terminal OH groups.
- Polyols are familiar to those skilled in the art and described for example in “Kunststoffhandbuch” [Plastics Handbook], volume 7, “Polyurethane” [Polyurethanes], Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1. Particular preference is given to polyetherols as the polyols used.
- Customary chain extenders or crosslinkers are optionally added to the named polyols during production of the isocyanate prepolymers. Such substances are known in principle from the prior art.
- the ratio of organic diisocyanates to polyols and optional chain extenders is preferably chosen such that the isocyanate prepolymer has an NCO content of 2% to 33.5%, preferably 10% to 32%, further preferably of 12% to 30%, and most preferably an NCO content of 15% to 28%.
- the diisocyanate composition in accordance with (iii) does not comprise a 30 prepolymer, with preference given, in the production of the thermoplastic polyamide, to the use of no prepolymers in the reaction of (i), (ii), and (iii).
- thermoplastic polyamide preferably uses no compound having free hydroxyl groups in the reaction of (i), (ii), and (iii); further preferably none of components (i), (ii), and (iii) contains free hydroxyl groups, further preferably none of components (i), (ii), and (iii) contains free hydroxyl groups and no further components having free hydroxyl groups are used.
- thermoplastic polyamide is obtainable or obtained through the reaction of at least the components (i), (ii), and (iii):
- the PTHF preferably has a number-average molecular weight Mn in the range from 500 to 3000 g/mol, further preferably in the range from 500 to 2000 g/mol.
- the components (i), (ii), and (iii) are preferably used in a molar ratio of [(i)+(ii)]:(iii) in the range from 10:1 to 1:10, preferably in the range from 5:1 to 1:5, further preferably in the range from 2:1 to 1:2, further preferably in the range from 1.5:1 to 1:1.5, further preferably in the range from 1.2:1 to 1:1.2, further preferably in the range from 1.1:1 to 1:1.1, further preferably in the molar ratio [(i)+(ii)]:(iii) of 1:1.
- the molar ratio (i):(ii) is preferably in the range from 10:1 to 1:10, preferably in the range from 5:1 to 1:5, further preferably in the range from 2:1 to 1:2, further preferably in the range from 1.5:1 to 1:1.5, further preferably in the range from 1.2:1 to 1:1.2, further preferably in the range from 1.1:1 to 1:1.1, further preferably 1:1.
- a catalyst having a Lewis base component preferably a catalyst selected from the group consisting of N-methylimidazole, melamine, guanidine, cyanuric acid, dicyandiamide, and mixtures thereof, further preferably at least N-methylimidazole.
- the product may be extended or crosslinked with a polyisocyanate or polyepoxide, with use of a difunctional crosslinker preferred. If, for example, recycling can be avoided, use of a higher-functional crosslinker is also possible.
- a polymers having terminal NCO groups preference is given to using epoxides such as bisphenol A derivatives or aliphatic diepoxides and, in the case of terminal acid groups, to diisocyanates such as MDI.
- the invention likewise relates to a process for producing a thermoplastic polyamide, in particular a thermoplastic polyamide, comprising the reaction of at least the following components:
- composition comprising a polymeric compound having two carboxylic acid moieties
- the composition in accordance with (i) comprises 95% by weight, preferably 99% by weight, of one or more polymeric compounds each having two carboxylic acid moieties, based on the total weight of the composition in accordance with (i).
- the dicarboxylic acid composition in accordance with (ii) comprises 95% by weight, preferably 99% by weight, of one or more dicarboxylic acids and/or dicarboxylic anhydrides, based on the total weight of the dicarboxylic acid composition in accordance with (ii).
- the diisocyanate composition in accordance with (iii) comprises 95% by weight, preferably 99% by weight, of one or more diisocyanates, based on the total weight of the diisocyanate composition in accordance with (iii).
- the composition comprising a polymeric compound having two carboxylic acid moieties in accordance with (i) is obtained or obtainable through the reaction of the components (ia) and (ib):
- the polymeric compound having two carboxylic acid moieties preferably has no free hydroxyl groups other than the OH groups present in the COOH groups.
- a diol composition comprising a dihydric polyester diol or polyether diol is used.
- Suitable dihydric polyester diols are known per se to those skilled in the art.
- Polyester diols may be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
- dicarboxylic acids examples include: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids may be used either individually or in admixture with one another.
- the free dicarboxylic acids it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylate esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides.
- dicarboxylic acid mixtures of succinic acid, glutaric acid, and adipic acid in quantity ratios of, for example, 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
- dihydric alcohols examples include: ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol. Preference is given to using ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. It is also possible to use polyester diols derived from lac-tones, for example ⁇ -caprolactone, or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid.
- the polyester diols may be prepared by polycondensation of the organic, for example aromatic and preferably aliphatic dicarboxylic acids and/or derivatives and dihydrc alcohols without catalyst or preferably in the presence of esterification catalysts, ideally in an atmosphere of inert gas, for example nitrogen, carbon monoxide, helium, argon, etc., in a melt at temperatures of 150 to 250° C., preferably 180 to 220° C., optionally under reduced pressure, down to the desired acid number which is preferably less than 10, more preferably less than 2.
- inert gas for example nitrogen, carbon monoxide, helium, argon, etc.
- the esterification mixture undergoes polycondensation at the above-mentioned temperatures down to an acid number of 80 to 30, preferably 40 to 30, under standard pressure and subsequently under a pressure of less than 500 mbar, preferably 50 to 150 mbar.
- esterification catalysts that may be used are iron catalysts, cadmium catalysts, cobalt catalysts, lead catalysts, zinc catalysts, antimony catalysts, magnesium catalysts, titanium catalysts, and tin catalysts in the form of metals, metal oxides or metal salts.
- the polycondensation may also be carried out in the liquid phase in the presence of diluents and/or entraining agents, for example benzene, toluene, xylene or chlorobenzene, for removal of the water of condensation by azeotropic distillation.
- diluents and/or entraining agents for example benzene, toluene, xylene or chlorobenzene
- the organic dicarboxylic acids and/or derivatives and dihydric alcohols advantageously undergo polycondensation in a molar ratio of 1:1 to 1.8, preferably 1:1.05 to 1.2.
- the polyester diols used have a functionality of 2 and, for example, a number-average molecular weight of 480 to 3000 g/mol, preferably 1000 to 3000 g/mol.
- Suitable dihydric polyether polyols are known per se to those skilled in the art.
- Polyetherols are prepared by known processes, for example by anionic polymerization with alkali metal hydroxides or alkali metal alkoxides as catalysts and with addition of at least one starter molecule comprising 2 to 8 reactive hydrogen atoms in bonded form, or through cationic polymerization with Lewis acids such as antimony pentachloride or boron fluoride etherate or through bases, for example potassium hydroxide, from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
- Suitable alkylene oxides are, for example, 1,3- and 1,2-propylene oxide, 1,2- and 2,3-butylene oxide, and ethylene oxide.
- tetrahydrofuran monomer may be used.
- the dihydric polyester diol or polyether diol which comprises the diol composition in accordance with (ia), is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyadipates, polycarbonates/polycarbonate diols, and polycaprolactones and polytetrahydrofuran (PTHF), preferably PTHF, with the PTHF preferably having a number-average molecular weight Mn in the range from 500 to 3000 g/mol, further preferably in the range from 500 to 1500 g/mol.
- PTHF polytetrahydrofuran
- a dicarboxylic acid composition comprises one or more dicarboxylic acids and/or one or more dicarboxylic acid derivatives.
- dicarboxylic acid preference is given to organic dicarboxylic acids having 2 to 12 carbon atoms, further preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms.
- dicarboxylic acids that may be used are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids may be used either individually or in admixture with one another.
- the free dicarboxylic acids it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylic anhydrides, which may likewise be used individually or in admixture with one another, and also mixtures comprising free dicarboxylic acids and dicarboxylic acid derivatives.
- the dicarboxylic acid composition in accordance with (ib) comprises at least one dicarboxylic acid or one dicarboxylic anhydride, with the dicarboxylic acid or dicarboxylic anhydride preferably selected from the group consisting of C2 to C12 dicarboxylic acids and the anhydrides thereof, further preferably from the group consisting of C4 to C8 dicarboxylic acids and the anhydrides thereof, further preferably at least 1,4-butanedioic acid (succinic acid) and succinic anhydride.
- the composition comprising a polymeric compound having two carboxylic acid moieties in accordance with (i) comprises at least one polyester dicarboxylic acid, polycarbonate dicarboxylic acid or polyether dicarboxylic acid, with the polyester, polycarbonate or polyether component preferably selected from the group of dihydric polyesters, polycarbonates, and polyethers, preferably from the group consisting of polyethylene glycol, polypropylene glycol, polyadipates, polycarbonates/polycarbonate diols, and polycaprolactones and polytetrahydrofuran (PTHF), preferably PTHF, with the PTHF preferably having a number-average molecular weight Mn in the range from 500 to 3000 g/mol, further preferably in the range from 500 to 2000 g/mol.
- PTHF polytetrahydrofuran
- the polymeric compound having two carboxylic acid moieties comprises preferably at least HOOC—(CH 2 ) x O-PTHF-OOC—(CH 2 ) y —COOH, where x and y are independently an integer in the range from 1 to 10, preferably in the range from 1 to 5, further preferably in the range 1 to 3, with the polymeric compound having two carboxylic acid moieties further preferably comprising at least HOOC—(CH 2 ) 2 —COO-PTHF-OOC—(CH 2 ) 2 —COOH.
- a dicarboxylic acid composition is likewise used, with the dicarboxylic acid composition comprising one or more dicarboxylic acids.
- the dicarboxylic acid preference is given to organic dicarboxylic acids having 2 to 12 carbon atoms, further preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms.
- dicarboxylic acids that may be used are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids may be used either individually or in admixture with one another.
- the dicarboxylic acid composition in accordance with (ii) comprises at least one dicarboxylic acid, preferably selected from the group of C2 to C12 dicarboxylic acids, further preferably from the group of C4 to C8 dicarboxylic acids, further preferably at least 1,6-hexanedioic acid (adipic acid).
- a diisocyanate composition is used.
- the diisocyanate composition here comprises at least one diisocyanate.
- the diisocyanate composition may also comprise two or more diisocyanates.
- Diisocyanates that may be used are aliphatic, cycloaliphatic, araliphatic, and/or aromatic diisocyanates.
- aromatic isocyanates 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocyanate (TDI), 4,4′-, 2,4′-, and/or 2,2′-diphenylmethane diisocyanate (MDI), mixtures of 2,4′- and 4,4′-diphenylmethane diisocyanate, urethane-, carbodiimide- or uretonimine-modified liquid 4,4′- and/or 2,4-diphenylmethane diisocyanate, 4,4′-diisocyanatodiphenylethane, mixtures of monomeric methylene diphenyl diisocyanates, and higher polycyclic homologs of methylene diphenyl diisocyanates (polymeric MDI), (1,2) and 1,5-naphthylene diisocyanate.
- TDI 2,4-tolylene diisocyanate
- MDI 4,4′-, 2,4′
- Aliphatic diisocyanates used are customary aliphatic and/or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta-, and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and/or 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-, 2,4′- and/or 2,2′-dicyclohexylmethane diisocyanate.
- the diisocyanate composition in accordance with (iii) comprises at least one diisocyanate selected from the group consisting of 2,2′-diphenylmethane diisocyanate (2,2′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), hexamethylene 1,6-diisocyanate (HDI), and 4,4′-, 2,4′-, and 2,2′-methylenedicyclohexyl diisocyanate (H12MDI), naphthylene diisocyanate NDI, tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), para-diphenyl diisocyanate (PDI), preferably at least MDI.
- 2,2′-diphenylmethane diisocyanate (2,2′-MDI)
- aromatic diisocyanates are used.
- the use of an aromatic diisocyanate yields partially aromatic amide block copolymers with further-improved thermal stability.
- the diisocyanate composition in accordance with (iii) may also be used in the form of a prepolymer, preferably a prepolymer having two free isocyanate groups, derived from at least one diisocyanate and at least one polyol, preferably a polyol having two terminal hydroxyl groups.
- a prepolymer allows the additional incorporation of urethane groups into the block copolymer in controllable proportions, through which it is possible, for example, to modify the properties of the polymer or increase its molecular weight.
- Diisocyanate prepolymers are obtainable by reacting an excess of the above-described diisocyanates, for example at temperatures from 30 to 150° C., preferably at temperatures from 50 to 120° C., most preferably at approximately 80° C., with polyols to form the prepolymer.
- the preparation of the prepolymers according to the invention is preferably carried out using diisocyanates and commercially available polyols based on polyesters, derived for example from adipic acid, or polyethers, derived for example from ethylene oxide and/or propylene oxide, with the polyols preferably having two terminal OH groups.
- Polyols are familiar to those skilled in the art and described for example in “Kunststoffhandbuch” [Plastics Handbook], volume 7, “Polyurethane” [Polyurethanes], Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1. Particular preference is given to polyetherols as the polyols used.
- Customary chain extenders or crosslinkers are optionally added to the named polyols during production of the isocyanate prepolymers. Such substances are known in principle from the prior art.
- the ratio of organic diisocyanates to polyols and optional chain extenders is preferably chosen such that the isocyanate prepolymer has an NCO content of 2% to 33.5%, preferably 10% to 32%, further preferably of 12% to 30%, and most preferably an NCO content of 15% to 28%.
- the diisocyanate composition in accordance with (iii) does not comprise a prepolymer, with preference given, in the production of the thermoplastic polyamide, to the use of no prepolymers in the reaction of (i), (ii), and (iii).
- thermoplastic polyamide preferably uses no compound having free hydroxyl groups in the reaction of (i), (ii), and (iii); further preferably none of components (i), (ii), and (iii) contains free hydroxyl groups, further preferably none of components (i), (ii), and (iii) contains free hydroxyl groups and no further components having free hydroxyl groups are used.
- thermoplastic polyamide comprises the reaction of at least the components (i), (ii), and (iii):
- the PTHF preferably has a number-average molecular weight Mn in the range from 500 to 3000 g/mol, further preferably in the range from 500 to 2000 g/mol.
- the components (i), (ii), and (ii) are preferably used in a molar ratio of [(i)+(ii)]:(iii) in the range from 10:1 to 1:10, preferably in the range from 5:1 to 1:5, further preferably in the range from 2:1 to 1:2, further preferably in the range from 1.5:1 to 1:1.5, further preferably in the range from 1.2:1 to 1:1.2, further preferably in the range from 1.1:1 to 1:1.1, further preferably in the molar ratio [(i)+(ii)]:(iii) of 1:1.
- the molar ratio (i):(ii) is preferably in the range from 10:1 to 1:10, preferably in the range from 5:1 to 1:5, further preferably in the range from 2:1 to 1:2, further preferably in the range from 1.5:1 to 1:1.5, further preferably in the range from 1.2:1 to 1:1.2, further preferably in the range from 1.1:1 to 1:1.1, further preferably 1:1.
- a catalyst having a Lewis base component preferably a catalyst selected from the group consisting of N-methylimidazole, melamine, guanidine, cyanuric acid, dicyandiamide, and mixtures thereof, further preferably at least N-methylimidazole.
- components (i) and (ii) are brought into contact and then component (iii) is added.
- the reaction of the components (i), (ii), and (iii) takes place in a reactive extruder apparatus comprising at least two, preferably interconnected, extruders, preferably in a tandem reactive extruder.
- the carbon dioxide formed during the reaction is removed, resulting in an unfoamed polyamide, or the carbon dioxide formed during the reaction is used as a blowing agent for foaming, resulting in a foamed polyamide.
- the product may be extended or crosslinked with a polyisocyanate or polyepoxide, with use of a difunctional crosslinker preferred. If, for example, recycling can be avoided, use of a higher-functional crosslinker is also possible.
- a polymers having terminal NCO groups preference is given to using epoxides such as bisphenol A derivatives or aliphatic diepoxides and, in the case of terminal acid groups, to diisocyanates such as MDI.
- the invention additionally relates to a thermoplastic polyamide obtained or obtainable by the process described above.
- the invention relates to the use of a thermoplastic polyamide as described above or of a thermoplastic polyamide obtained or as described above for the production of a molded body, an injection-molded product, an extrusion product, a film, an extruded foam or a foam article.
- the invention relates to the use of a thermoplastic polyamide as described above or of a thermoplastic polyamide obtainable or obtained by a process as described above for an article selected from the group of tubing, in particular pressure tubing, and cable sheathing.
- the invention relates to the use of a foam article obtained or obtainable from a thermoplastic polyamide as described above or of a thermoplastic polyamide obtainable or obtained by a process as described above for an article selected from the group consisting of footwear soles; footwear sole components, in particular footwear midsoles; items of sports equipment, in particular balls; and damping elements, in particular damping elements for a machine or for an automobile.
- the invention relates to a tandem reactive extruder, comprising
- first zone additionally comprises structures in which there is at least one further additional zone upstream and/or downstream of the first zone, wherein “downstream of the first zone” at the same time means “upstream of the second zone”.
- second zone additionally comprises structures in which there is at least one further additional zone upstream and/or downstream of the second zone, wherein “upstream of the second zone” at the same time means “downstream of the first zone” and “downstream of the second zone” at the same time means “upstream of the third zone”.
- third zone additionally comprises structures in which there is at least one further additional zone upstream and/or downstream of the third zone.
- the first extruder 1 comprises at least one further zone downstream of the first zone and upstream of the second zone.
- the inlet in the third zone of the second extruder 2 is connected to the outlet in the second zone of the first extruder 1.
- the connection linking the inlet in the third zone of the second extruder 2 and the outlet in the second zone of the first extruder 1 is designed to allow material to pass from the first zone into the third zone of the second extruder.
- the first extruder comprises inlet orifices in the first and second zones.
- the second extruder comprises inlet orifices in at least the first and second zones.
- zones optionally present upstream or downstream optionally have inlet orifices and/or outlet orifices through which materials may be added or removed.
- the respective first and second zones are temperature-controllable, likewise the third zone, and it is further preferable if the respective first and second zones and the third zone are temperature-controllable, likewise any further zones optionally present upstream or downstream.
- Reactive extruder having a tandem assembly of two extruders, with each extruder having a multiplicity of separate, temperature-controllable zones (tandem reactive extruder).
- the tandem reactive extruder comprises a first, zoned, temperature-controllable extruder (extruder 1) that includes an extruder screw, a jacket covering the at least one extruder screw, and at least two zones comprising a first zone, a second zone downstream of the first zone, and an outlet in the second zone; and a second, zoned, temperature-controllable extruder (extruder 2), with extruder 2 including an extruder screw, a jacket covering the one extruder screw, and at least three zones comprising a first zone, a second zone downstream of the first zone, a third zone downstream of the second zone, and an inlet in the third zone; and an extruder die head downstream of the third zone, with the inlet in the third zone of the second extruder 2 being connected to the outlet in the second zone of the first extruder
- the first extruder has inlet orifices in the first and second zones through which materials are (able to be) added.
- the second extruder likewise has inlet orifices in at least the first and second zones through which materials are (able to be) added.
- the connection linking the inlet in the third zone of the second extruder 2 and the outlet in the second zone of the first extruder 1 allows the substance (mixture) obtained in the second zone of the first extruder 1 to pass into the third zone of the second extruder 2, where it comes into contact with the substance (mixture) from the second extruder 2 obtained in the second and/or third zone and is preferably mixed there.
- a schematic representation of a tandem reactive extruder assembly is shown in FIG. 1 .
- a polymeric compound having two carboxylic acid moieties in this case HOOC—(CH 2 ) 2 —COO-PTHF-OOC—(CH 2 ) 2 —COOH, was prepared by reacting the polyol with succinic anhydride.
- succinic anhydride for this, a 20-liter reactor fitted with a reflux condenser was charged under a nitrogen atmosphere with 8 kg of polytetrahydrofuran having a molecular weight Mw of 1000 g/mol and heated to 130° C. with stirring.
- a twice-molar amount (1602 g) of solid succinic anhydride (Mw 100.07 g/mol) was added to the reactor.
- the succinic anhydride melted in the PTHF, after which the reactor contents were heated to 200° C. and held at this temperature, with stirring, for at least 1 hour.
- the succinic anhydride reacted with the free OH groups of the PTHF with ring opening and the formation of ester bonds.
- the samples were prepared using two extruders in a tandem assembly (tandem reactive extruder) as follows: The adipic acid was added in the first extruder 1 in the first zone (in this case: zone 1, region of heating element 1 of extruder 1), melted, and mixed with the HOOC—(CH 2 ) 2 —COO-PTHFOOC—(CH 2 ) 2 —COOH from 3.1 in a second zone (in this case: zone 3 of the first extruder for sample 1 and sample 3, addition of the HOOC—(CH 2 ) 2 —COO-PTHFOOC—(CH 2 ) y —COOH in the region of heating element 5 of extruder 1).
- Antifoam and catalyst were added in the first zone (zone 1) of the second extruder (in the region of heating element 1 of extruder 2) and, for sample 1 and sample 3, the MDI was added in the second zone (in this case: zone 2) of the second extruder (region of heating element 2 of extruder 2).
- zone 2 region of heating element 2 of extruder 2
- the MDI had already been added in the first zone (in this case: zone 1) of the first extruder; the formulation was analogous to sample 3.
- the throughput was ⁇ 10 kg/h throughout and the extruder speed of the two extruders was 200 rpm.
- Table 1 The formulations in each case are shown in Table 1.
- the temperature profile of the first and second extruder (extruder 1, extruder 2) is shown in Table 2.
- the samples were investigated by GPC and IR spectroscopy.
- the GPC data show that adequate molecular weights were achieved and that polymers had consequently been obtained.
- Table 3 shows the molecular weights for samples 1, 2, 3, and 7.
- the IR spectra show the clear presence of amide structures for all four samples.
- FIG. 1 shows a reactive extruder having a tandem assembly of two extruders, with each extruder having a multiplicity of separate, temperature-controllable heating elements (tandem reactive extruder).
- the tandem reactive extruder comprises a first, zoned, temperature-controllable extruder (extruder 1) that includes the at least one extruder screw (not shown), a jacket covering the at least one extruder screw, and at least two zones comprising a first zone (1-1), a second zone downstream of the first zone (1-2), and an outlet in the second zone; and a second, zoned, temperature-controllable extruder (extruder 2), with extruder 2 including an extruder screw (not shown), a jacket covering the one extruder screw, and at least three zones comprising a first zone (2-1), a second zone downstream of the first zone (2-2), a third zone downstream of the second zone (2-3), and an inlet in the third zone; and an extruder die head downstream of the third zone (2-E), with the
- the first extruder has inlet orifices in the first and second zones through which materials are (able to be) added.
- the second extruder likewise has inlet orifices in at least the first and second zones through which materials are (able to be) added.
- the connection linking the inlet in the third zone of the second extruder 2 and the outlet in the second zone of the first extruder 1 (1-2) allows the substance (mixture) obtained in the second zone of the first extruder 1 to pass into the third zone of the second extruder 2 (2-3), where it comes into contact with the substance (mixture) from the second extruder 2 obtained in the second and/or third zone and is preferably mixed there.
- first extruder 1 a further zone (X) downstream of the first zone and upstream of the second zone, with the first zone (1-1) and zone (X) representing a melting zone (1-A).
- the further part of extruder 1 leading from (1-2) is the initial mixing zone (1-B).
- a mixing zone (2-B) is shown; also shown is a reaction zone (2-C) leading from the inlet/leading from the connection between the outlet from the first extruder and the inlet of the second extruder (D).
- Discharge, i.e. extrusion, of the resulting thermoplastic polyamide takes place via the extruder die head (2-E) of the second extruder 2.
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US4129715A (en) * | 1977-06-03 | 1978-12-12 | The Upjohn Company | Polyester amides suitable for injection molding |
US4420602A (en) * | 1982-09-27 | 1983-12-13 | The Upjohn Company | Melt-polymerization process for the preparation of thermoplastic polyamides and polyesteramides |
US4672094A (en) * | 1986-01-21 | 1987-06-09 | The Dow Chemical Company | Method for increasing the molecular weight of polyamides and polyesteramides |
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